Aqueous dispersion of carbon black



Patented July it, flfil d UNHTEED T il eliififiw AQUEUUS DIISPEREKQN QAEEBDN ELAGISZ No Drawing. Application November 28, 1935-3.

Serial No. Wies l i4 (or. rec nt) This invention relates to the dispersion of car-' bon black in anaqueous medium, and generally comprises the use of a dispersing agent of the general structure obtained by condensing a naphthalene sulfonic acid, or a homoloque or derivative thereof, with formaldehyde, or its equivalent, a process and a produce thereof, all as hereinafter more fully described and claimed.

There are many industrial applications of carbon black which require its suspension or dispersion in an aqueous medium. Thus, for example, it is frequently used as a pigment in the preparation of black paper or paper-like materials in which case the carbon black may be slurried in water and added as a paste or thin slurry to the stock in a paper beater. In this manner carbon black is commonly added to aqueous slurries of asbestos which are to be used for the manufacture of asbestos board, gasket materials, and the like. Aqueous dispersions of carbon black are frequently added ,to rubber latex to provide a compounding and pigmenting agent for the rubber constituent thereof. Black concrete or cement is commonly prepared by mix:- ing carbon black with the cement or mortar when in the wet state. Furthermore, it has been proposed, and the process presents much promise,

to use a dispersion of carbon black in an aqueous medium as a printing ink in place of the printing inks ordinarily used consisting of carbon black and asuitable oil. M

The dispersion of carbon black in water presents clifilculties, however, and these dimculties have militated against its more general and otherwise advantageous use. If carbon black is stirred into water, it will be found that the particles are not readily wet by the water and, once wetted, they tend to cling together, i. e. agglomerate, and do not disperse in the aqueous medium as colloidal particles of carbon black.

These non-wetting and non-dispersing characteristics constitute serious disadvantages in the practical use of carbon black when suspended in Water because carbon black is generally used for its tinctorial power; and, as is well known and recognized, the tinctorial power of a finely divided material is proportional to the size of the individual particles and the completeness with which they are dispersed.

Attempts have been made to overcome the stated difiiculties by adding certain protective colloids to the water in which the carbon black was to be suspended. For this purpose there have been employed soaps, such as sodium stealate or oleate, and proteins, such as casein, hemoglobin, or alen. While these agents are gen-- erally very efiective to disperse most finely di vided pigments in water, carbon black. presents unusual difiiculties and is not particularly well dismrsed by them. This is believed to be due to the fact that carbon black particles are very much smaller than, in fact of a different order of magnitude from that of. the particles of ordinary pigments. Furthermore, soaps and proteins are in themselves attended with certain disadvantages. In order to be effective they must be used in relatively large quantities; and, furthermore, they lose their efiectiveness and are precipitated when brought in contact with acid. environments or the ions of heavy metal salts. The latter disadvantages render soaps or proteins particularly ineffective to disperse carbon black in water for use in cement or mortar; or in paper-making when an acid or alum size is employed; or for use with aqueous slurries of asbestds such as are commonly encountered in the manufacture of asbestos board, gasket material, and the like, which slurries, owing to the inherent chemical nature of the asbestos, always contain calcium and magnesium ions. Eilrnllarly, dispersions of carbon black in water prepared with the aid of soaps or proteins are also espeoial- 1y ineffective for use in connection with the general process described in my Patent No. 1,956,053, issued April 24, 1934, in which a watery slurry of asbestos is treated with an aqueous dispersion of electropositlve rubber particles which dispersion may be acid in reaction or may contain poly valent metal ions.

An object of this invention is to provide a sus pension of carbon black in water in which the carbon black is more completely dispersed and which therefore possesses greater tinctorial power than has heretofore been possible. All other object or the invention to provide a dis= persion of carbon black in water which is not .readily aggregated or fiocculated by acids or polyvalent metal ions such as are provided by the acid sizes employed in paper-making; by the asbestos of asbestos-water slurries employed in heretofore been attainable. Other objects and advantages of the invention will become apparent with its more detailed description.

I have discovered that the disadvantages of the prior art are overcome and the foregoing objects are attained if carbon black is dispersed in water containing dissolved therein a. small quantity of one or more members of the class of aromatic compounds of the general structure obtained by condensing sulfonic acids of naphthalene. its homologues or derivatives, with formaldehyde or its equivalent. These compounds may be looked upon as derivatives of polynaphthyl alkyls or their homologues and may be expressed by the general graphical formula in which A and A designate two or more aromatic groups-which may or may not be alike; which contain naphthalene rings joined to an aliphatic nucleus R which may consist of a single alkyl group or a plurality of alkyl groups associated in straight chain or branched chain formation; and in which SOaM designates at least one free sulfonic acid group or at least one sulfonic acid group in combination with a. soluble salt-forming radical. The members of the class may be synthesized either by direct sulfonation of a hydrocarbon or a derivative thereof which possesses the necessary configuration of at least two naphthalene rings joined to an aliphatic nucleus, or, as is usually more convenient and commercially practical, by causing a naphthalene sulfonic acid or a homologue or derivative thereof to react with formaldehyde or its equivalent, preferably in the ratio of approximately two mols of aromatic sulfonic acid for each mol of aldehyde. The member of the family which I generally employ because it is cheap and very effective for present purposes may be obtained by condensing beta-naphthalene sulfonic acid with formaldehyde. While the beta-naphthalene sulfonic acid condensation product may be prepared in known ways, I find that the product obtained by the following procedure possesses highly satisfactory properties for use in practicing my invention.

To 100 parts of concentrated sulfuric acid (specific gravity 1.84) contained in a suitable sulfonator and maintained at 160 C. are added slowly with stirring 100 parts of refined naphthalene. After all of the naphthalene has been introduced (this operation generally requires about one hour), the mass is stirred at 160 C. for four hours longer or until a test shows that substantially none of the naphthalene remains unsulfonated. The sulfonation mixture is then cooled to about 100 C. and diluted with 44 parts of water to prevent solidification on subsequent cooling. The diluted material is further cooled to C. at which temperature 12 parts of a 40% aqueous solution of formaldehyde are added. This mixture is then stirred for three hours longer at 80 C.; but at the end of each successive hour there are added 12 parts more of formaldehyde solution, making a total at the end of the three hours of four portions or 48 parts in all. After all the formaldehyde has been added, the temperature is progressively raised over a period of one hour to -100 C. where it is maintained for 18 hours, While the mass is constantly stirred, oruntil the control test described later on in this specification shows that a product of optimum effectiveness has been obtained. Experience has shown that when pure naphthalene is used, a final heating period of 18 hours yields the best product. Soon after the temperature has been raised to 95-100" 0., it is found that substantially none of the aldehyde remains unconsumed in the condensation reaction. During the later stages of the 18-hour heating period, the mixture progressively thickens until at the end it generally reaches the consistency of thick molasses. If this thickening be comes so great, however, as to prevent proper stirring, a small quantity of water may be added to keep the material liquid. After the heating is completed, the mixture is cooled, neutralized with a suitable alkali, e. g. sodium hydroxide, and, if desired, dried. It is then ready for use.

A somewhat purer and better product can be obtained by diluting the viscous reaction mass with about three times its volume of water (the amount is not important so long as it is sufficient to permit convenient handling in thesubsequent filtering operation), and neutralizing with lime. For the latter purpose I generally use an aqueous paste or suspension of hydrated or slaked lime. The neutralized slurry is filtered hot to remove the calcium sulfate precipitate which forms from the interaction of the lime and sulfuric acid unconsumed in the sulfonation reaction; and to the filtrate is added the requisite amount of sodium carbonate quantitatively to convert the calcium salt of the desired sulfonic acid into its sodium salt. The resulting calcium carbonate precipitate may then be removed by filtration and the filtrate which contains the desired ingredient evaporated to dryness according to any of the well known drying procedures.

The sulfonation of the naphthalene may be conducted in a cast iron vessel; but the reaction with formaldehyde is preferably carried out in enameled or lead-lined apparatus.

A cheap grade of crude naphthalene which contains other aromatic hydrocarbons as impurities may be employed in the foregoing detailed procedure without sacrifice of desirable qualities. The substitution of an alkylated naphthalene, e. g. a methyl naphthalene or an ethyl naphthalene, for naphthalene itself results in a product which is particularly effective for present purposes. Such alkylated products, however, which are especially effective for use in the broader aspects of this invention, may be objectionable for some purposes because, due to their tendency to reduce the surface tension of water, they promote the formation of foam in the carbon black dispersion. Materials made from aromatic compounds which are free from substituting alkyl groups have substantially no tendency to reduce the surface tension of water; and for this reason carbon black dispersions prepared with them do not have the undesirable tendency to form foam possessed by aqueous dispersions of carbon black prepared with the aid of prior agents which, unlike present materials, generally rely for their effectiveness on their ability to reduce the surface tension of water. The product obtained as described above by the reaction of naphthalene sulfonic acid with formaldehyde is specifically recommended for use in a preferred form of this invention where the tendency to produce foam is objectionable.

In the chemical reaction which occurs between an aromatic sulfonic acid and formaldemolecular Weight is necessary to yield the best results for present purposes as determined according to the indicated empirical test given later on in this specification; but this theory forms no part of my definition and I do not desire to be bound by it.

Whereas I generally use the sulfonic acids of the herein defined class in the form of their sodium salts, any water-soluble salt or derivative, or even the free acid, may be employed. Salts of monovalent metals, particularly the alkali metals, are preferable, however, to salts of polyvalent metals.

In accordance with the present invention aqueous dispersions of carbon black may be prepared by merely stirring the material into a solution of the effective agent. This mixing operation is conveniently carried out in a tank provided with a suitable agitator; but if maximum dispersion of the carbon black in highest concentration is to be obtained, the mixing should be carried out in a ball or so-called colloid mill.

If maximum dispersing effect is to be obtained, a solution should, in general, be used for preparing the mixture which contains a quantity of dispersing agent equal to about 4% of the weight of the carbon black employed. In this connection, however, it may be said further that different kinds of carbon black require difierent quantities of dispersing agent under otherwise like conditions to produce an optimum dispersing effect. With most carbon blacks the optimum dispersing effect will be obtained when a quantity of dispersing agent equal to 2-6% of the weight of carbon black is employed; but some samples, 1. e. those of extremely small particle size, require a minimum of 4-8% to produce the best result. It is believed that the relative quantity of dispersing agent essential to produce a given result is dependent on the size and/or specific surface of the carbon black particles to be dispersed. This is in accord with the observation that a thermatomic carbon black which possesses an ultra-microscopic particle size requires for a unit weight a larger quantity of dispersing agent to produce a given result than does a carbon black known to be of larger particle size. If a larger quantity of dispersing agent is employed than that necessary to produce the optimum result with any given carbon black, the excess of dispersing agent does no material harm but is of no advantage. The minimum quantity of agent required to produce the optimum result may readily be determined by trial. For example, 25-gram portions of the carbon black to be tested may be vigorously stirred into 75-cubic-centimeter portions of solutions containing, respectively, 1, 1 and 2 grams of the dispersing agent. The minimum quantity of agent essential to produce a paste having the maximum fluidity or least viscosity should be chosen. As previously stated, this test is also useful to ascertain and control the optimum degree of polymerization of products made according to the general procedure given above as well as to determine the relative value for present purposes of any 'material which falls within the scope of the appended claims.

In thepractice of this invention instead of mixing the carbon black with a solution of the dispersing agent, carbon black may be mixed with the dispersing agent in the dry and powdered state and the resulting dry mixture may be stirred into water or an aqueous medium, the dispersing agent dissolving in the watery liquor to provide the desired peptizing influence. While this process has advantages for some purposes, it does not, however, give as good a result as is obtained by mixing the carbon black into a previously prepared solution of dispersing agent; and it is necessary to use a relatively larger quantity of dispersing agent to produce in like degree the dispersing effect that would be obtained by stirring the carbon black into a solution containing a lesser quantity oi dissolved dispersing agent.

When it is desired to produce relatively dilute dispersions of carbon black in water, it is usually desirable first to prepare a dispersion of the carbon black in high concentration and then to dilute with water to the desired value. This procedure is preferable both when the {black is stirred into a. solution of the dispera ngi agent and when a. dry. mixture 01 and dispersing agent is added to waters;

Carbon black dispersions prepared'in'nccordance with the present invention aremore fluid or plastic than dispersions similarly prepared but with the aid of no or other dispersing agents known to me. In this connection it may be said that different carbon blacks dispersed in an aqueous medium give dispersions exhibiting widely different consistencies at any given concentration. The process of the present invention will always yield, however, so iar as I am aware, a dispersion possessing greater fluidity or plasticity at any given concentration than can be obtained under like conditions with other dispersing agents. Dispersions of ordinary carbon black prepared in accordance with the present invention and containing as much as 25% by weight of dispersed material are quite fluid. Dispersions containing between 30 and 40% of carbon black are of more or less plastic or pasty consistency. However, it is possible with some carbon blacks to prepare in accordance with the present in-, vention dispersions containing from 40 to 50% of dispersed material which are of a smooth, pasty consistency. In the absence of any dispersing agent, or in the presence of most dispersing agents, it is not possible to 'go beyond 25-30% of carbon black without obtaining a dry crumbly product.

If a carbon black dispersion prepared in accordance with the present invention is diluted with water and examined under the microscope at a high magnification (900 diameters), minute particles will be observed suspended in the watery medium and engaging in rapid Brownian motion. In contradistlnction to dispersions generally prepared with the aid of other dispersing agents, it will be found that the addition of small quantitles of acids, or of salts providing heavy metal ions, to carbon black dispersions prepared according to the present invention will not markedly aggregate or fiocculate the dispersed particles thereof. This fact makes the process of this in-,

vention particularly valuable for dispersing carbon black in acid environments or in the presence of heavy metal ions normally coagulative of colloidally dispersed material.

The term "carbon black as employed herein is used in a broad generic sense which is intended to embrace finely divided carbon such as lamp black as well as the materials more commonly referred to as carbon blacks.

It should be understood that the present disclosure is for the purpose of illustration only and that this invention includes all modifications and equivalents which fall within the scope of the appended claims.

ocess of dispersing carbon black in an ac iedium which comprises agitating car- ?oo in an aqueous solution of a dispersing rained by condensing formaldehyde with a lo acid'of the naphthalene series, whereation of the normally aggregated partic c carbon black occurs, said agent being I 2. The process of dispersing carbon black inan aqueous medium which comprises agitating car-- bon blacl; in an aqueous solution of a dispersing agent comprising a sulfonic acid compound having at least naphthalene rings connected by a methylene nucleus, whereby deflocculation of the-normally aggregated particles oi carbon black occurs, said'agent being present in amount of .tiaily 2 to 8% based on the weight of the on black. e process of dispersing carbon black in eous medium which comprises agitating blacl: in an aqueous solution of a dispersnt comprising a salt oia compound ohi. 3' i condensing formaldehyde with an 1 tednsphthalene sulfonic acid,whereby dece flocculation of the normally aggregated particles of carbon black occurs, said agent being present amount of substantially 2 to 8% basedon the eight of the dry carbon black.

The process of dispersin carbon black in an 35 aqueous medium which comprises agitating carbon black in an aqueous solution of a dispersing agent comprising a salt of the product obtained by condensing substantially one mol of formaldehyde with substantially two mols of beta-naphthalene sulionic acid, whereby deflocculation of the *n aggregated particles of the carbon said agent being present in amount d lly 2 to 3% based on the weight or be .ilacic.

so position of matter, an aqueous c rbon black containing dissolved sodium dispersing agent comprising chic acid derivative of a compound having at least two naphthalene rings connected 50 by a methylene nucleus, said agent being present in amount of substantially 2 to 8% based on the weight or the dry carbon black.

i a new-composition of matter, dry carbon black in intimate admixture with substantially .2 to on the weight of the dry carbon or" a c, persion agent comprising a water- L sulionic acid derivative of a compound ring least two naphthalene rings connected agent coma. product from n amount of substantially 2 to 8% based assures the condensation of formaldehyde with a; sul ionic acid of the naphthalene series, said agent I being present in amount of substantially 2 to 8% based on the weight of the dry carbon black.

8. As a new composition of matter, dry carbon 5 black in intimate admixture with substantially 2 to 8% based on the weight of the dry carbon black of a dispersion agent comprising a. watersoluble salt of a condensation product resulting from the condensation of formaldehyde with .9 10 sulfonic acid of the naphthalene series.

, 9. As anew composition of matter, an aqueous dispersion of carbon black containing dissolved in the aqueous medium a dispersing agent comprising a condensation product resulting from the condensation of formaldehyde with an alkylated naphthalene sulfonic acid, said agent being present in amount of substantially 2 to 8% based on the weight of the dry carbon black.

10. As a new composition of matter, dry car- 8 bon black in intimate admixture with substan-- tially 2 to 8% based on the weight of the dry carbon black of a dispersion agent comprising a' water-soluble salt of a condensation product resulting from the condensation of formaldehyde with an 'alkylated naphthalene sulfonic acid.

11. As a new composition of matter, an aqueous dispersion of carbon black containing dissolved in the aqueous medium a dispersing agent comprising a condensation product resulting from the condensation of substantially one mol of formaldehyde with substantially two mols of beta-naphthalene sulfonic acid, said agent being present in'amount'of substantially 2 to 8% based 35,

on the weight of the dry carbon black.

12. As a new composition of mattendry car- 'bon black in intimate admixture with substantially 2 to 8% based on the weight of the dry carbon black of a dispersion agent comprising a water-soluble salt of a. condensation product re- 40 sulting from the condensation of substantially onemol of formaldehyde with substantially two mols of beta-naphthalene sulfonic acid.

13. A. water dispersable carbon black mixture comprising a pasty mass of carbon black, water in amount to produce a paste, and 2 to 8% based on the weight of the dry carbon black of a dispersing agent comprising the formaldehyde condensation product of a sulfonated naphthalene compound, said paste mixture upon dilution with water having the carbon black particles in colloidally dispersed condition.

14. A water dispersable carbon black mixture comprising a plastic mass of carbon black, water in amount to produce a plastic mixture, and 2 to 8% based on the weight or the dry carbon black of a dispersing agent comprising the formaldehyde condensation product of a sulfonated naphthalene compound, said plastic mixture upon dilution with water having the carbon black particles in colloidally dispersed condition.

GEORGE R. TUCKER. 

